The Effects of Modified Chitosan on the Physicomechanical Properties of Mortar

This paper reports a study on producing admixtures from chitosan (Ch) obtained from shrimp shell treatment. The admixtures (Ch-g-AA) were based on chitosan (Ch) and acrylic acid (AA) in the following composition ratios: 65/35, 50/50, and 35/65. The grafted copolymers were synthesized using grafting polymerization and potassium persulphate as the initiator. This study investigated the properties of mortars in the presence of grafted copolymers, including setting time, workability, water absorption, and compressive strength. The results showed that grafted copolymers premixed with mortar mixes improved the properties of the mortar. However, increasing the AA ratio in the grafted copolymer decreased the W/C ratio, setting time, and water absorption, whereas the fluidity and compressive strength increased.

Acrylic acid; Chitosan; Copolymer; Grafted; Mortar

        At present, research in the field of admixtures for construction materials based on polymeric compounds has gained increasing significance and attention (Ariffin et al., 2015; Ke, 2019). These compounds are used in various spheres as additives because they impart unique properties, including workability, compressive strength, durability, water/cement ratio, water absorption, and porosity (Mignon et al., 2016). Thus, polymers have become more monolithic regarding impermeability, frost resistance, and tensile strength. In addition, bending has increased in cement pastes, mortars, and concretes. Several researchers have investigated the effects of different polymers, including acrylic, polyurethane, epoxy, and chitosan, on the physicomechanical properties of cement pastes, mortars, and concretes (Negim et al., 2013; Bezerra, 2016; Bekbayeva, 2020a; 2020b). Chitosan (CS) is a polysaccharide composed of randomly distributed deacetylated (?-(1-4)-linked D-glucosamine) and acetylated units based on D-glucosamine (Pillai et al., 2009; Bezerra et al., 2011; Lasheras-Zubiate et al., 2011; Vys?var?il and Z?iz?lavsky?, 2017). Polymeric resins are chosen according to mortar type based on several factors, including functional groups, polymer types, molar ratio, pH, viscosity, and polymer dosage (Ukrainczyk and Rogina, 2013; Govin et al., 2016; Wuju et al., 2020). The presence of amino groups in chitosan enables its use in many applications, including bio cement, dental bio cement, and additives to cement-based materials. The effects of chitosan and chitosan derivatives on the properties of cements and mortars have been reported. For example, Lasheras-Zubiate et al. (2012) studied the effects of the addition of two nonionic chitosan derivatives (hydroxypropyl and hydroxyethyl chitosan) and one ionic derivative (carboxymethyl chitosan) on the properties of cement mortar. Ionic chitosan derivatives were more effective than nonionic derivatives, acted as good thickeners, and reduced the workability of cement mortar because of the delay in the hydration of cement particles. Ustinova and Nikiforova (2016) investigated the effects of hydroxypropyl chitosan on cementitious materials and found that viscosity and water retention values increased. However, when used in lime mortars, it showed the same results but with lower efficiency (Z?iz?lavsky? et al., 2019). Yulia and Tamara (2016) reported that chitosan added to cement did not reduce the cement’s strength compared with a synthetic polymer additive based on polyethylhydrosiloxan. In addition, the amount of chitosan (0.6–1.0% based on cement mass) increased the resistance of the cement compositions to alternate freezing and thawing. Bezerra et al. (2011) reported that the utilization of chitosan as an admixture in cement paste reduced porosity, increased viscosity, and improved strength, whereas the addition of chitosan had an adverse impact on the properties of the cement. Shenghua et al. (2014) reported that chitosan modified by amidation and sulfonation through a reaction with maleic anhydride had a high water-reducing ratio, fluidity, and compressive strength at a low water/cement ratio. With the addition of latex and chitosan to concrete, compressive and tensile strengths decreased by 14% and 24%, respectively, compared with the control (Ulisses et al., 2011). The primary mechanism of the action of polymer additives in cement systems is that they form a polymer film on the surface of the grains of cement, sand, and capillaries, which promotes the adhesion of sand to cement particles (Negim et al., 2013; Santos et al., 2018; Muntohar et al., 2020). Thus, polymers have become more monolithic regarding impermeability, frost resistance, tensile strength, and bending increases in cement paste, mortar, and concrete. Bekbayeva et al. (2020a) modified chitosan by grafting with acrylic acid in different ratios to clarify the effects of three different composition ratios of chitosan-g-acrylic acid, P[Ch-g-AA], on the physical and mechanical properties of cement pastes. They found that as the AA ratios in the grafted copolymer increased, the water-to-cement (WC) ratio, setting time, and water absorption decreased. In contrast, compressive strength sharply increased at almost all hydration ages. Their work was further extended to investigate the effects of modified chitosan on the properties of mortar, which is the subject of the present investigation.

    The properties of mortar containing grafted copolymers were investigated. The grafted copolymers were based on the different composition ratios of Ch and AA. The results showed that the W/C ratio decreased as the AA ratio increased in the grafted copolymers. The compressive strength and workability of mortar premixed with grafted copolymers increased in the OH, NH, and COOH groups, and branched chains pierced the liquid phase to disperse the effects of copolymer particles among the cement particles. In addition, the setting times (initial and final) were lengthened, while water absorption decreased as the AA ratio increased in the grafted copolymers.

Athiyamaan, V., Ganesh, G.M., 2019. Analysis of the Alignment of Micro-Steel Fibers in Admixture-Based Self-Compacting Concrete (MSFR-SCC) using NDT and Evaluation of Its Effect on the Modulus of Rupture. International Journal of Technology, Volume 10(1), pp. 5–15

Ariffin, N.F., Hussin, M.W., Sam, A.R.M., Bhutta, M.A.R., Khalid, N.H.A., Mirza, J., 2015. Strength Properties and Molecular Composition of Epoxy?Modified Mortars. Constr. Build. Mater, Volume 94, pp. 315–322

ASTM C187, 2016. American Standard Test Method

ASTM C191, 2019. American Standard Test Method

ASTM C109/C109M?16a, 2016. Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2?in. or [50?mm] Cube Specimens). ASTM International: West Conshohocken, PA, USA

Bekbayeva, L., Negim, E.S., Yeligbayeva, G., Ganjian, E., 2020a. Modification of Chitosan as Chemical Admixture for Cement Pastes. Egyptian Journal of Chemistry, Volume 63(4), pp. 1497–1508

Bekbayeva, L., Negim, E., Gulzhakhan, Y., Ganjian, E., 2020b. Utilization of Poly(Polyvinyl Alcohol-g-2-Ethylhexyl Acrylate) as Admixture for Mortar. International Journal of Technology, Volume 11(2), pp. 259–268 

BS 882, 2016. British Standard Test. Aggregate for Concrete

BS EN 12350-5, 2019. British Standard Test. Method for Determination of Flow 

BS 1881-122, 2011. British Standard Test. Testing Concrete: Method for Determination of Water Absorption

Bezerra, U.T., 2016. Biopolymers with Superplasticizer Properties for Concrete. In: Biopolymers and Biotech Admixtures for Eco?Efficient Construction Materials. Woodhead Publishing Limited: Cambridge, United Kingdom, pp. 195–220

Bezerra, U.T., Ferreira, R.M., Castro-Gomes, J.P., 2011. The Effects of Latex and Chitosan Biopolymer on Concrete Properties and Performance. Key Engineering Materials, Volume 466, pp. 37–46

EN 197-1, 2011. British Standard Test. Cement, Composition, Specifications and Conformity Criteria for Common Cements

Fang, Y., 2018. Study on Effects of Molecular Structure of Polycarboxylate Superplasticizer on Adsorption and Hydration Properties. New Building Materials Mag., Volume 45, pp. 14–17

Guo, S., Lu, Y., Bu, Y., Li, B., 2018. Effect of Carboxylic Group on the Compatibility with Retarder and the Retarding Side Effect of the Fluid Loss Control Additive Used in Oil Well Cement. Royal Society Open Science, Volume 5(9), pp. 1–9

Govin, A., Bartholin, M.?C., Biasotti, B., Giudici, M., Langella, V., Grosseau, P., 2016. Modification of Water Retention and Rheological Properties of Fresh State Cement?based Mortars by Guar Gum Derivatives. Construction and Building Materials, Volume 122, pp. 772–780

Ghosh, P., Rameshbabu, A.P., Dogra, N., Dhara, S., 2014. 2,5-dimethoxy 2,5-dihydrofuran Crosslinked Chitosan Fibers Enhance Bone Regeneration in Rabbit Femur Defects. RSC Advances, Volume 4(37), pp. 19516–19524

Juntao, D., Jun, Z., Zhaohua, D., 2017. Effect of Superabsorbent Polymer on the Properties of Concrete. Polymer, Volume 9(12), pp. 1–17

Ke, Y., 2019. Preparation and Characterization of Early Strength Fast-setting Polycarboxylic Acid Water Reducer. New Building Materials Mag., Volume 8, pp. 5–8

Khalil, E.S., Saad, B., Negim, E.S.M., Saleh, M.I., 2015. Novel Water-soluble Chitosan Derivative Prepared by Graft Polymerization of Dicyandiamide: Synthesis, Characterisation, and Its Antibacterial Property. Journal of Polymer Research, Volume 22(6), pp. 1–12

Kusrini, E., Shiong, N.S., Harahap, Y., Yulizar, Y., Dianursanti, Arbianti, R., Pudjiastuti, A.R., 2015. Effects of Monocarboxylic Acids and Potassium Persulfate on Preparation of Chitosan Nanoparticles. International Journal of Technology, Volume 6(1), pp. 11–21

Kim, Y.Y., Lee, K.M., Bang, J.W., Kwon, S.J., 2014. Effects of W/C Ratio on Durability and Porosity in Cement Mortar with Constant Cement Amount. Advance in Material Science and Engineering, Volume 2014, pp. 1–11

Lasheras-Zubiate, M., Navarro-Blasco, I., Ferna?ndez, J.M., A?lvarez, J.I., 2011. Studies on Chitosan as an Admixture for Cement-based Materials: Assessment of Its Viscosity Enhancing Effect and Complexing Ability for Heavy Metals. Journal of Applied Polymer Science, Volume 12, pp. 242–252

Li, M., Liu, J., Hu, Y., Gao, X., Yuan, Q., Zhao, F., 2020. Investigation of the Specularite/Chlorite Separation using Chitosan as a Novel Depressant by Direct Flotation. Carbohydrate Polymers, Volume 240, https://doi.org/10.1016/j.carbpol.2020.116334

Lasheras?Zubiate, M., Navarro?Blasco, I., Ferna?ndez, J.M.M., A?lvarez, J.I.I., 2012. Effect of the Addition of Chitosan Ethers on the Fresh State Properties of Cement Mortars. Cement and Concrete Composites, Volume 34, pp. 964–973

?ukowski, P., Woyciechowski, P., Adamczewski, G., Rudko, M., Filipek, K., 2015. Curing of Polymer–Cement Concrete: Search for a Compromise. Advanced Materials Research, Volume 1129, pp. 222–229

Mignon, A., Snoeck, D., D’Halluin, K., Balcaen, L., Vanhaecke, F., Dubruel, P., Van Vlierberghe, S., De Belie, N., 2016. Alginate Bi?opolymers: Counteracting the Impact of Superabsorbent Polymers on Mortar Strength. Construction and Building Materials, Volume 110, pp. 169–174

Moodi, F., Kashi, A., Ramezanianpour, A.A., Pourebrahimi, M., 2018. Investigation on Mechanical and Durability Properties of Polymer and Latex-Modified Concretes. Construction and Building Materials, Volume 191, pp. 145–154

Muntohar, A.S., Diana, W., Tafalas, M.Y., Bimantara, N.R., 2020. The Behavior of the Flexible Plate – Supported with SiCC-Mortar Column on Expansive Soil. International Journal of Technology, Volume 11(1), pp. 123–132

Negim, E.S., Khatib, M.J., Nurlan, O.I., 2013. Effect of Acrylate Copolymers on the Rheological Properties of Portland Cement Mortar Pastes, Part III. World Applied Sciences Journal, Volume 23(4), pp. 549–553

Negim, E.S., Aisha, A.M.B., Yessimkanova, U., Kurmanbekova, A., Tyazhina, K., Urkimbaeva, P.I., Rakhmetullayeva, R.K., Shatabayeva, E., Irmukhametova, G., Mun, G.A., Yeligbayeva, G. Zh., Khatib, J.M., 2015. The Effect of Terpolymer Admixtures on Physico-mechanical Properties of Cement Pastes. International Journal of Basic and Applied Sciences, Volume 4(1), pp. 10–18

Negim, E.S., Khatib, J.M., Sakhy, M., Shilibekov, S., Shanshabayev, N., Jakiyayev, B., 2014. The Effect of pH on Physico-Mechanical Properties of Cement Pastes Containing Poly (Acrylate) Latexes: Chemical Admixtures. World Applied Sciences Journal, Volume 29(6), pp. 796–804

Pillai, C.K.S., Paul, W., Sharma, C.P., 2009. Chitin and Chitosan Polymers: Chemistry, Solubility and Fiber Formation. Progress in Polymer Science, Volume 34, pp. 641–678

Pradeep, K., Yahya, E.C., Lisa, C.D.T., Girish, M., Dinesh, N., Viness, P., 2012. Novel High-Viscosity Polyacrylamidated Chitosan for Neural Tissue Engineering: Fabrication of Anisotropic Neurodurable Scaffold via Molecular Disposition of Persulfate-Mediated Polymer Slicing and Complexation. International Journal of Molecular Sciences, Volume 13, pp. 13966–13984

Santos, A.R., Veiga, M.D.R., Santos Silva, A., de Brito, J., A?lvarez, J.I., 2018. Evolution of the Microstructure of Lime-based Mortars and Influence on the Mechanical Behaviour: The Role of the Aggregates. Construction and Building Materials, Volume 187, pp. 907–922

Shenghua, L., Jingjing, L., Qingfang, Z., Huang, L., Sun, T., 2014. Synthesis of Modified Chitosan Superplasticizer by Amidation and Sulfonation and Its Application, Performance and Working Mechanism. Industrial & Engineering Chemistry Research, Volume 53, pp. 3908?3916

Ustinova, Y.V., Nikiforova, T.P., 2016. Cement Compositions with the Chitosan Additive. Procedia Engineering, Volume 153, pp. 810–815

Ulisses, T.B., Rui, M.F., Joa?o, P.-G., 2011. The Effect of Latex and Chitosan Biopolymer on Concrete Properties and Performance. Key Engineering Materials, Volume 466, pp. 37–46

Ukrainczyk, N., Rogina, A., 2013. Styrene?butadiene Latex Modified Calcium Aluminate Cement Mortar. Cement and Concrete Composites, Volume 41, pp. 16–23

Vys?var?il, M., Z?iz?lavsky?, T., 2017. Effect of Chitosan Ethers on Fresh State Properties of Lime Mortars. In: IOP Conference Series. Materials Science and Engineering, Bristol, Volume 251(1), pp. 1–8

Wuju, X., Changlong, W., Xuefei, L., Jiye, L., Desheng, X., Yang, L., 2020. Effect of Functional Superplasticizers on Concrete Strength and Pore Structure. Applied Sciences, Volume 10(10), pp. 1–16

Yulia, V.U., Tamara, P.N., 2016. Cement Compositions with the Chitosan Additive. Procedia Engineering, Volume 153, pp. 810–815

Z?iz?lavsky?, T., Vys?var?il, M., Bayer, P., Rovnani?kova?, P., 2019. Impact of Guar Gum and Chitosan Ethers on Physico?mechanical Properties and Durability of Natural Hydraulic Lime Mortars. In: Proceedings of the 5^th Historic Mortars Conference. RILEM Publications S.A.R.L.: Paris, France, pp. 1279–1290